Manufacture of vat dyestuffs of the anthraquinone series



Patented May 5, 1931 ca rn STATES PATENT OFFICE IvIAX ALBERT KUNZ, IVLANNHEIM, GERMANY, ASSIGNOR TO GENERAL ANILINE \VOEKS, INQ, OF NEVT YORK, N. Y., A CORPORATION OF DELAWARE MANUFACT'URE OF VAT DYESTUEFS OF THE ANTHRAQUINONE SERIES No Drawing. Original application filed February 9, 1926, Serial No. 87,173, and inGermany February 16 1925. Divided and'this application filed. February 29, 1925.; Serial No. 258,143.

The subject-matter of this application has of excellent fastness are obtained by con- (lensing aldehydes ot the anthraquinone se ries with amino-anthraquinones or their substitution products. The reaction products are azo-methlnes corresponding to the geneand A are the same or difierent anthraquinone radicles, OllllBlWlSB substituted or I have, further found that it is often ad o H 0 (i 0110 N ti ll ll o o cting with anthraquinone aldehydes not on the free amino-anthraqulnones but on thelr which are easily obtainable, forexample, by condensing {l111l1'l0-{LI1l3l1lfflC1LllI10118S wlth aldereaction the aryl-aldehyde residue is replaced by the anthraqulnone aldehyde radicle. The

are difiiculties in the direct production of the new dyestufis with a free amino-anthraral formula A CH=NA in which A not. i

vantageous to prepare the new dyestufis by azo-methine derivativesof the aryl series liydes of the benzene series. In the second said reaction is of special value in case there CuBs quinone, 'for example on account of the amino-anthraquinone being diflicultly soluble.

It is to be understood that I do not claim here the-process of producinv vat dyestuffs by condensing aldehydes of the anthraquinone series with free amino-anthraquinones or their substitution products.

The following examples will further illustrate how my invention may be carried out in practice, to which examples, however, the invention is not limited. The parts are by weight, if not otherwise stated.

Example 1 56 parts of Q-benzylidene-amino-anthraforms a brown powder which is soluble in the usual organic solvents with a brown color. With alkaline hydrosulfite, a dark brownish violet vat is formed from which cotton is dyed fast orange shades.

Example 2 59 parts of 2-11nthraquinone-aldehyde, 1000 parts of nitrobenzene and 86 parts of l-chlor-Q-benzylidene amino anthraquinone are'boiled for hour. The dyestu'ff obtained according to the equation:

+ oinsono is a brownish yellow powder melting above 350 .C., and which dyes cotton from a violetblack vat fast orange shades.

Ewample 5 118- parts of 2-anthraquinone-aldehyde are dissolved in 1500 parts, by volume, of boiling nitrobenzene and mixed with a hot solution o CH=N r of 104 parts of 2'.6-dibenzylidene-diaminoanthraquinone in 1000 parts, by volume, of nitrobenzene. After boiling for some minutes, a yellow precipitate separates from the brown solution, which precipitate, after the mixture is cooled, is filtered 0H and Washed. The dyestuif obtained according to the equation:

CeH5 0 0 t H t C -on0 N 2 v o c i! ll ll on O 0 Cnllzs dyes cotton from an olive-black vat yellow shades of excellent fastness.

Cl 0 NHz (IJH l H A CHO N ll ll Ewample 4 by washing and oxidation in the air, is altered to a strong claret red of excellent fastness.

7 Example 5 125 parts of 1-a1nino-2-anthraquinonealdehyde, 3000 parts, by volume, of nitrobenzene and 175 parts of 2-(o-cl1lor-benzylidene-ainino)-anthraquinone are boiled for hour. The product obtained according to the equation:

is Worked up in the usual manner. It is idenmeal with that obtained according to the fore going example.

Example 6' 62.5 parts of l-ainin0-2-anthraquinouealdehyde, 1500 parts, by volume, of nitrobenzene and 86.5 parts of 1-chlor-2-benzylidenea1nino-anthraquinone are heated to forms a reddish brown powder melting at 348 to 349 degrees centigrade. Vith alkaline hydrosulfite, it forms an olive-black vat from which cotton is dyed the same shade which,

boiling for 1 hour and Worked up as usual. The dark reddish brown product obtained according to the equation:

C0115 O NH: Cl ll l II o olmono lll) -' examples.

4. solution of 41.4 parts of 2.6-dibenzylidene- 0 o I i (l I r e r C OHO N V OH=N 2 \C/ V \C/ R C 6 II II on 0 o i forms a reddish brown loosepowder melting above 350 C. and dyeing cotton from a violet-black vat fast claret shades.

melts at 352 to 354 degrees centigrade, and the dyeings produced with this dyestufl are I claret red.

Example '1" Example 9 A mixture of 126 parts of 1-amino-2- anthraquinone-aldehyde, 3000 parts, by volume, of nitrobenzene and 163 parts of 2-benzyli dene amino 3 methyl-anthraquinone is boiled for hour. The product obtained according to the equation:

A hot solution of 10 1 parts of 2.6-dibenzylidene-diamino-anthraquinone in 1000 parts, -by.volume,of nitrobenzene is introduced into a boiling solution of 135 parts of 1-chlor-2- anthraquinone aldehydeV in 1500 parts, by

Colin is Worked up as described in the foregoing A chocolate brown crystalline powder is obtained which melts above 340 C. and dyes cotton from an olive-black vat fast pink shades.

volume, of nitrobenzene. After some minutes, a fine crystalline yellow precipitate is separated from the boiling solution. The new product obtained according to the equation:

Cam

3 f CH a? 1 v r 2 o11o II\IT C /C r R 0 c1 0 0/ 1 I 0/ CH=N I 5 (l i l) ('11 i \C/ v E Emample melts above 360 C. and dyes cotton from a dark olive-brown vat yellow shades of excellent fastness.

What I claim is: V p The process of producing new compounds of the anthraquinone series which comprises acting with an anthraquinone aldehyde on a condensation product of an amino-anthra-V quinone with an aldehyde of the benzene series.

In testimony whereof I have hereunto set my hand.

A boiling solution of 502 parts of l-amino- Q-anthraquinone-aldehyde in 1000 parts, by volume, of nitrobenzene is mixed with a hot diamino-anthraquinone in 400 parts, by volume, of nitrobenzene. Almost immediately a voluminous reddish brown precipitate is separated from the boiling solution, which precipitate, after cooling, is filtered oil and finished in the usual manner. The very pure product obtained according to the equation:

MAX ALBERT KUNZ.

-NH2 I O NH2 

